Partially hydrolyzed, poly(N-acyl)alkylenimines in personal care

ABSTRACT

Partially hydrolyzed, poly(N-acyl)alkylenimines), and novel nitrogen-substituted derivatives thereof, provide useful and improved personal care compositions and processes.

BACKGROUND OF THE INVENTION

1. Field Of The Invention

This invention relates to poly(N-acyl alkylenimines) in personal care,and more particularly to partially hydrolyzed, poly(N-acylalkylenimines), and to nitrogen-substituted derivatives thereof, and topersonal care compositions and processes using such polymers.

2. Descrption Of Background Information

Various cationic polymeric components used in personal care providedesirable managing characteristics when applied to keratinoussubstrates. For example, cationic celluloses have been found to exhibitsuperior conditioning and substantivity to keratinous substrates, aswell as other properties significant for personal care utility. Variouscationic cellulosics, however, provide limited solubility in nonaqueoussystems and provide limited stability under certain pH conditions,consequently limiting their applicability to certain personal careapplications. Cationic polyvinyl pyrrolidones exhibit good solubilitybut are relatively limited in conditioning ability with respect to theconditioning ability provided by existing cationic celluloses.Copolymers of acrylamide and dimethyl, diallyl ammonium chloride alsoprovide utility in personal care including good solubility, but cancontain residual monomers deleterous in personal care applications.

Poly(N-acyl alkylenimines) have been used in personal care applications.U.S. Pat. No. 3,579,630 (Herz et al.) discloses hair dressingformulations with poly(N-acyl ethylenimine) homoand copolymers. Thepoly(N-acyl alkylenimines) described in the Herz et al. patent arenonionic polymers, and as such do not provide significant substantivityto keratinous substrates thereby limiting their utility in personal careapplications.

Various poly(alkylenimines), and processes for producing such polymers,are disclosed in U.S. Pat. No. 3,833,521 (Karbstein et al.), U.S. Pat.No. 4,161,581, (Wagner et al.), U.S. Pat. No. 4,492,788 (Cooke), WestGerman Published Patent Application No. 1,720,436 (Seeiger et al. I) andWest German Published Patent Application No. 1,720,437 (Seeliger et al.II).

There is a need, however, for a class of polymers having utility inpersonal care which exhibit both substantivity and flexibility incombination with a desirable balance of additional properties useful inpersonal care applications. It would also be desirable if such a classof polymers provide additional utility including: solubility in waterand other hydrophilic solvents; film strength and gloss; moistureretention; low solution viscosity; as well as additional propertiesenabling widespread utility in a variety of personal care applications.

SUMMARY OF THE INVENTION

Personal care compositions are provided comprising carrier and aneffective managing amount of partially hydrolyzed poly(N/acylalkylenimine). The poly(N-acyl alkylenimine) contains repeating unitsrepresented by the structural formula: ##STR1## wherein a is form about1 to about 50 mole percent. For each repeating unit individually, inthis formula: Q is an anion; R₁ is hydrogen, alkyl, aryl, alkaryl oraralkyl; R₂ is hydrogen or a hydrocarbyl-containing group; R₃ ishydrogen, oxygen or a hydrocarbyl-containing group; v is equal to thevalence of Q; x is 2 or 3; and y is 0 or 1; and z is 0 or 1; with theprovisos that: (1) when R₃ is oxygen and y is 0, R₂ is ahydrocarbyl-containing group and z is 1; and (2) when R₃ is not oxygenthen y is 1.

A process for producing such compositions is provided which comprisesproviding carrier with an effective managing amount of such poly(N-acylalkylenimine).

A process for managing keratinous substrate is also provided whichcomprises applying an effective managing amount of such poly(N-acylalkylenimine) to the sbustrate.

Nitrogen substituted, partially hydrolyzed, poly(N-acyl alkylenimines)are also provided which have the structural formula and parameters ofthe previous formula with the further provisos that:

(1) when all R₂ and R₃ groups are hydrogen then the average value of zper repeating unit is greater than 0 and Q represents a mixture ofanions; and

(2) when all z values are 0 then at least one R₃ group is ahydrocarbyl-containing group.

DETAILED DESCRIPTION OF THE INVENTION

The partially hydrolyzed, poly(N-acyl alkylenimines) of this inventionprovide significant and improved utility in personal care applications.The partially hydrolyzed, poly(N-acyl alkylenimines) of this inventioncan be tailored to provide desirable: solution viscosities; solubilitiesin water and other hydrophilic solvents; compatibilty with a broadspectrum of surfactants; substantivity; equilibrium moisture content;stability; film-forming properties; low toxicity and/or otherperformance characteristics, making such polymers eminently suitable ina wide variety of personal care applications.

Partially hydrolyzed, poly(N-acyl alkylenimines) of this invention areprepared by the partial hydrolysis of poly(N-acyl alkylenimine)precursors containing repeating units represented by the structuralformula: ##STR2## wherein n is at least about 200, and most preferablyfrom about 500 to about 200,000, and most preferably from about 2,000 to10,000.

In formula I, for each repeating unit individually, the R₁ group in theacyl substituent is hydrogen, alkyl, aryl, aralkyl or alkaryl group. TheR₁ group will generally have form one to about 12 carbon atoms. SuitableR₁ groups include, but are not limited to: methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, t-butyl, n-dodecyl, benzyl, phenyl,methylphenyl, and the like. The R₁ group is preferably hydrogen or alinear or branched, saturated, aliphatic alkyl group containing from oneto about 3 carbon atoms, and is most preferably ethyl.

In Formula I, for each repeating unit individually, the extent of thealkylene group, defined by x, is 2 or 3, and is most preferably 2.

The poly(N-acyl alkylenimines) precursors, as well as partiallyhydrolyzed or nitrogen-substituted derivatives thereof, possess terminalgroups, not shown in the formulas. These terminal groups are notcritical and generally are the residue groups normally provided duringpolymerization while producing the poly(N-acyl alkylenimine) precursors,or which may be provided by terminal group substitution, followingestablished procedures. Typically, poly(N-acyl alkylenimine) terminalgroups include, but are not limited to, hydrogen, hydrocarbyl, halogenand terminal groups as provided in U.S. Pat. No. 4,161,581 and thereferences cited therein.

A particularly preferred poly(N-acyl alkylenimine) precursor ispoly(N-propionyl ethylenimine), for when R₁ is ethyl and x is 2, whichcontains repeating units represented by the structural formula: ##STR3##wherein n is as defined previously.

The poly(N-acyl alkylenimine) precursors are commercially available ormay be derived by the polymerization of oxazolines. Such polymerizationprocedures are well established in the art, such as described in U.S.Pat. No. 3,579,630 (Herz et al.) and U.S. Pat. No. 4,492,788 (Cooke).

The hydrolyzing agent used to hydrolyze the poly(N-acyl alkylenimines)precursor may be either an acid or base, and is preferably an acid. Thehydrolyzing agent may be any acid or base having sufficient strength toeffect partial hydrolysis of the poly(N-acyl alkylenimine) precursorunder appropriate hydrolyzing conditions.

Suitable hydrolyzing agents include, but are not limited to: mineralacids, such as sulfuric acid, sulfonic acid, hydrochloric acid,hydrobromic acid, phospheric acid, nitric acid, and the like or mixturesthereof; bases such as sodium hydroxide, potassium hydroxide, and thelike or mixtures thereof; and other known hydrolyzing agents or mixturesthereof.

Preferred hydrolyzing agents include: hydrochloric acid, phosphoricacid, sulfuric acid, and most preferably, concentrated hydrochloricacid.

The hydrolysis reaction is generally conducted in the presence of asuitable solvent capable of providing a reaction medium for thepoly(N-acyl alkylenimine) precursor and hydrolyzing agent. Typicalsolvents include, but are not limited to, aqueous solutions; i.e.,having water as solvent; organic solvents, such as ethanol; and otherknown solvents; or mixtures thereof.

The amount of poly(N-acyl alkylenimine) precursor provided in a reactionmedium for hydrolysis is not critical. Generally, the concentration ofpoly(N-acyl alkylenimine) precursor will range from about 5 to about 50,preferably from about 10 to about 40, and most preferably from about 20to about 30 weight percent of the total weight of the reaction mixture.

The amount of hydrolyzing agent provided is not critical so long as aneffective hydrolyzing amount is provided sufficient to partiallyhydrolyze the poly(N-acyl alkylenimine) precursor. The amount ofhydrolyzing agent may be stoichiometrically equivalent to or greaterthan the desired extent of hydrolysis.

The relative proportion of hydrolyzing agent to poly(N-acylalkylenimine) precursor is not critical so long as sufficienthydrolyzing agent is provided to effect partial hydrolysis of thepoly(N-acyl alkylenimine) precursor. Generally, the amount ofhydrolyzing agent provided will range from about 0.05 to about 1,preferably from about 0.08 to about 0.5, and most preferably from about0.1 to about 0.3 moles per mole of poly(N-acyl alkylenimine) repeatunits.

Optional adjuvants may be provided to the reaction mixture, generallyafter hydrolysis, following procedures well established in the art.Typical adjuvants include: stabilizers; biocides, such as methylparaben;buffers; and other known adjuvants.

The hydrolysis reaction is conducted under conditions sufficient toeffect partial hydrolysis of the poly(N-acyl alkylenimine) precursor.Hydrolysis may be achieved following procedures well established in theart, such as described in U.S. Pat. No. 4,492,788 (Cooke) and WestGerman Published Patent Application No. 1,720,437 (Seeliger et al. II).

The particular process conditions and steps for conducting thehydrolysis reaction of this invention are not critical so long as theyare sufficient to effect partial hydrolysis.

The hydrolysis temperature will typically range from about 80° C., toabout 160° C., preferably from about 90° C. to about 120° C., and mostpreferably from about 100° C. to about 110° C. The hydrolysis pressuremay be at, above or below atmospheric pressure, and is generally atleast atomspheric, preferably from atmospheric to about 500 psig, and ismost preferably from atmospheric up to about 20 psig.

The time required for conducting the partial hydrolysis will varydepending upon the particular poly(N-acyl alkylenimine) precursor andconcentration thereof, the particular hydrolyzing agent andconcentration thereof, and various process conditions. Generally, thepartial hydrolysis will take at least about 2 hours, preferably fromabout 6 hours to about 20 hours, and most preferably from about 8 hoursto about 12 hours.

Once the desired degree of partial hydrolysis is achieved the partiallyhydrolyzed, poly(N-acyl alkylenimine) product is recovered, includingusing known recovery procedures, the procedures described in thisapplication, or both.

Partially hydrolyzed, poly(N-acyl alkylenimine) produced in any form maybe purified, concentrated, otherwise treated or untreated, using wellestablished procedures, to recover the desired form of partiallyhydrolyzed, poly(N-acyl alkylenimine) product.

If heat is used to assist the hydrolysis process, the product solutionmay be cooled to ambient temperature prior to recovery. Alternatively,the product solution may be adjusted to a combination of high basicityand high temperature sufficient to provide a precipitate of free amineof the partially hydrolyzed, poly(N-acyl alkylenimine). This precipitatemay be separated from the solution to provide purified, partiallyhydrolyzed, poly(N-acyl alkylenimine) in the free amine form as a solid,or when cooled as a liquid.

Recovery of the partially hydrolyzed, poly(N-acyl alkylenimine) as amixed quaternary ammonium salt may be achieved by neutralizing theproduct solution. When the hydrolyzing agent is an acid the neutralizingagent would be a base, and correspondingly when the hydrolyzing agent isa base the neutralizing agent would be an acid. Typical and preferredneutralizing agents include the hydrolyzing agents listed previously andother known hydrolysis neutralizing agents. Mixed quaternary ammoniumsalts of poly(N-acyl alkyenimine) may be recovered directly afterneutralization while in solution without additional purification steps.

Partially hydrolyzed, poly(N-acyl alkylenimine) polymer so producedcontains repeating units representing the structural formula: ##STR4##

The proportion of hydrolyzed alkylenimine repeating units in thepartially hydrolyzed, poly(N-acyl alkylenimine) of Formula III, definedby a, is generally from about 1 to about 50, preferably from about 3 toabout 30, and most preferably from about 5 to about 20 mole percent.

In Formula III, substituents defined by the parameters, Q, v and y maybe the same for each repeating unit throughout the polymer or may bedifferent from the corresponding substituent in other repeating units.For each repeating unit individually in Formula III the parameters aredefined as follows.

Quaternary ammonium salts of the partially hydrolyzed, poly(N-acylalkylenimines) of Formula III are provided when Q groups are present,i.e., when y is 1. Q is an anion, including mono-or divalent organic orinorganic anions. Suitable anions include, but are not limited to, oneor more of the following: organic anions such as carboxylates includingpropionate, butyrate, formate, benzoate and the like; inorganic anionssuch as halides including chloride, bromide and iodide; sulfonates;sulfates; phosphites; phosphates; phosphonates; carbonates; nitrates;and the like. Particularly preferred anions include chloride,proprionate and mixtures thereof. The Q anionic group may be provided byan acid hydrolyzing, or acid neutralizing, agent or by the hydrolyzedacylate group. Anionic groups may also be provided by an ion exchangemechanism or other known processes.

The N-acyl substituent of the partially hydrolyzed, poly(N-acylalkylenimines) of Formula III, defined by R₁, is the same, generally andpreferably, as the R₁ group defined previously for the poly(N-acylalkylenimine) precursor of Formula I.

The valence of the anion Q of the partially hydrolyzed, poly(N-acylalkylenimines) of Formula III, defined by v, determines the relativeproportion of anion to quaternary ammonium cation, in inverseproportion. The value of v will typically be 1 or 2, and is preferably 1thereby providing an equivalent molar amount of anion to quaternaryammonium cation. The average value of v per repeating unit containinganion may be greater than or equal to one for partially hydrolyzed,poly(N-acyl alkylenimines) containing a mixture of ions of differentvalences.

The length of the alkylene chain in the partially hydrolyzed,poly(N-acyl alkylenimines) of Formula III, defined by x, is the same asx as defined previously for the poly(N-acyl alkylenimines) precursor ofFormula I.

The presence or absence of quaternization in the backbone of thepartially hydrolyzed, poly(N-acyl alkylenimines) of Formula III isdefined by y. When y is 0 free amine is provided. When y is 1 quaternaryammonium, cationic nitrogen is provided. When all values of y are 0 thetotally free amine form of partially hydrolyzed, poly(N-acylalkylenimines) is provided. When all values of y are 1 the fullyquaternized form of partially hydrolized, poly(N-acyl alkylenimine) isprovided. When the average value of y per repeating unit is greater than0 and less than 1 both free amine and quaternary ammonium nitrogen atomsare provided within the polymer.

Following neutralization the partially hydrolyzed, poly(N-acylalkylenimine) will generally contained salt by-product. The level ofsalt contained in the product may be calculated as ranging from about 1to about 20, and is preferably up to about 7 weight percent of the totalproduct obtained in solution. Such salt can be retained or be removed bypurification procedures well established in the art.

In a typical embodiment, the hydrolysis procedure involves either of twoprocedures. In a first procedure the hydrolysis involves: (a) dissolvingthe poly(N-acyl alkylenimine) precursor in water, or other solvent, atthe desired weight percent; (b) heating the solution to the desiredreaction temperature; (c) adding the acidic hydrolyzing agent; (d)holding the reaction temperature for a specified period of time; (e)cooling to below about 60° C.; (f) neutralizing to pH 6.5-7.0 withaqueous alkaline solution; (g) clarifying the solution; (h) generallyadding preservative to thereby yield the desired concentration ofpartially hydrolyzed, poly(N-acyl alkylenimine) as a mixed quaternaryammonium salt in solution. In a second procedure the hydrolysis involvesusing the previously identified steps (a) through (d) for hydrolysisfollowed by: (e') causticizing to above pH 10 with aqueous alkalinesolution, at or slightly below the reaction temperature; (f') separatingthe solid and liquid phases; (g') cooling to below about 60° C., (h')diluting the solution to the desired polymer concentration; (i')clarifying the solution; (j') generally adding preservative; to therebyyield the partially hydrolyzed, poly(N-acyl alkylenimine) in a freeamine form having a reduced level of impurities.

Derivatives of partially hydrolyzed, poly(N-acyl alkylenimines) areprovided by reacting the hydrolyzed, free amine present in the partiallyhydrolyzed, poly(N-acyl alkylenimine) of Formula III, with or withousome quaternary ammonium substitution present, to provide oxygen orhydrocarbyl-containing substituents on the hydrolyzed nitrogen. Suchpartially hydrolyzed, poly(N-acyl alkylenimines) derivative will containrepeat units represented by the structural formula: ##STR5## wherein A,Q, R₁, v, x, and y are defined in Formula III. Some or all of thehydrogen on the nitrogen substituent will be replaced with (1) oxygen,as one or more R₃ groups; (2) hydrocarbyl-containing groups as one ormore R₂ or R₃ groups, or both; or (3) both (1) and (2).

Derivatized nitrogen substituents, defined by R₂ and R₃ in Formula IV,are provided when the hydrogen substituents on the nitrogen atom arereplaced with oxygen or any hydrocarbyl-containing group. Suitablehydrocarbyl-containing groups include, but are not limited to: alkyl,aryl, aralkyl, alkaryl, or alkyloxy groups containing one or more carbonatoms. Such hydrocarbyl-containing groups may be: linear, branched, orcyclic; saturated, unsaturated, or aromatic; and unsubstituted orsubstituted with functional groups such as hydroxyl, amino, ammonio,carboxyl, carboxylate, sulfonate, other known functional groups, ormixtures thereof. The derivatized nitrogen substituents may containionic groups providing the partially hydrolyzed, poly(N-acylalkylenimine) derivatives with other ionic substitution, providingdicationic or amphoteric poly(N-acyl alkylenimine) derivatives whenhydrolyzed nitrogen in the polymer backbone is present in thequaternized form.

In Formula Iv, the presence or absence of the R₂ group as well as ofquaternization in the backbone of the partially hydrolyzed, poly(N-acylalkylenimines) derivatives, defined by z, depends upon the type ofderivatization present. When R₃ is oxygen the y is 0, R₂ ishydrocarbyl-containing group and z is 1. When R₃ is not oxygen then yis 1. When all R₂ and R₃ groups are hydrogen then the average value of zper repeat unit is greater than 0 and Q represents a mixture of anions,i.e., more than one type of anion is provided per polymer molecule. Whenall z values are 0 then at least one R₃ group in thenitrogen-substituted, partially hydrolyzed, poly(N-acyl alkylenimine) isa hydrocarbyl-containing group.

Oxidized derivatives of partially hydrolyzed, poly(N-acyl alkylenimines)contain repeating units represented by the structural formula: ##STR6##wherein a, R₁ and x are as defined in Formula III and, for eachrepeating unit individually, R₂ is a hydrocarbyl-containing group asdefined for R₂ in Formula IV.

Partially hydrolyzed, poly(N-acyl alkylenimine) of Formula IV havingtertiary amine hydrolyzed nitrogen, i.e., where R₂ ishydrocarbyl-containing, can be oxidized to the corresponding amine oxidederivative, defined by Formula V, i.e., where R₃ is oxygen, at one ormore hydrolyzed nitrogen, using any known amine oxidizing agentfollowing established procedures. Suitable oxidizing agents include, butare not limited to: acyl-, aryl- or alkyl-containing hydroperoxides orperoxides; hydrogen peroxide; ozone; or mixtures thereof. Preferredoxidizing agents include: hydrogen peroxide and other common oxidizingagents.

Any derivatization capable of providing a suitable nitrogen substituentcontaining a hydrocarbyl group can be conducted. Such derivatizationreactions include, but are not limited to: alkylation, including the useof substituted or unsubstituted, hydrocarbyl halides, halohydrins,epoxides or other known alkylating agents; acylation, including the useof substituted or unsubstituted, acyl halides, esters, acid anhydrides,oxazolines, caprolactams or other known acylating agents; sulphonation,including the use of substituted or unsubstituted sulphonyl halides orother known sulphonating agents; carbamoylation, including the use ofhaloformates or other known carbamoylating agents; formation of ureasand thioureas, including the use of isocyanates, isothiocyanates orother known (thio)urea forming agents; and other amine derivatizationreactions, including mixtures of such agents.

Typical derivatization include, but are not limited to, the followingreactions.

The partially hydrolyzed, poly(N-acyl alkylenimine) of Formula III maybe derivatized by alkylation by reacting the hydrolyzed nitrogen with,for example, an alkyl-containing halide or epoxide to provide nitrogensubstitution wherein: R₂, R₃ or both are alkyl-containing groups, y isone, and Q is a halide. For example, reaction of the polymer withhalohydrins or 1,2 epoxides provides hydroxy substituted, nitrogensubstituents. Suitable alkylating agents include, but are not limited toone or more of the following: halohydrins such as3-chloro-2-hydroxypropyl trimethyl ammonium chloride,3-chloro-2-hydroxypropyl dimethyldodecyl ammonium chloride,3-chloro-2-hydroxypropyl dimethyloctadecyl ammonium chloride,3-chloro-2-hydroxypropyl- dimethyloctyl ammonium chloride, and the like;and their corresponding 1-2 epoxides such as 2,3-epoxypropyl trimethylammonium chloride, and the like; halohydrin sulfonates such asmonochlorohydrin sulfonate; and other alkylating agents for secondaryamines known in the art. Preferred alkylating agents include:3-chloro-2-hydroxypropyltrimethyl ammonium chloride,3-chloro-2-hydroxypropyl dimethyldodecyl ammonium chloride,3-chloro-2-hydroxypropyl dimethyltetradecyl ammonium chloride,3-chloro-2-hydroxypropyl dimethylhexadecyl ammonium chloride,3-chloro-2-hydroxypropyl dimethyloctadecyl ammonium chloride,monochlorohydrin sulfonate and the like.

The partially hydrolyzed, poly(N-acyl alkylenimine) of Formula III mayalso be derivatized by suitable reaction of the polymer withheterocyclic compounds such as oxazoline, caprolactam, other knownheterocyclic compounds, or mixtures thereof, to providenitrogen-substitution containing a substituent primary amine. Thederivatives containing such pendant nitrogen substituents can undergofurther derivatization reactions of the substituent primary amine,following established procedures.

The partially hydrolyzed, poly(N-acyl alkylenimine) may also bederivatized through crosslinking by providing a crosslinker reactivewith the hydrolyzed nitrogen. The crosslinker may be any suitablepolyfunctional compound which reacts with the hydrolyzed nitrogen amineof the unsubstituted or nitrogen-substituted, partially hydrolyzed,poly(N-acyl alkylenimine). The crosslinker may be represented by thestructural formula:

    R--(z).sub.m                                               (VI)

wherein m is at least 2, and preferably from 2 to 6.

In Formula VI, R is a polyvalent, substituted or unsubstituted, alkyl,cycloalkyl, aryl, alkaryl or aralkyl containing group having at least 1,preferably from about 2 to about 15 carbon atoms. Such R groups can beunsubstituted hydrocarbyl-containing groups or may contain hetero atoms.Suitable R groups include, but are not limited to, one or more of thefollowing: heterocyclics, such as substituted triazines includinghexamethylol melamine residues, ureas including bis(N,N-hydroxymethyl,methyl)urea residues; or other heterocyclics; alkylenes, such asmethylene, ethylene, propylenes, 2-hydroxy-propylenes, cycloakylenes,such as cyclohexylenes; alkarylenes, such as 2,2-bis(p-hydroxyphenyl)propane, xylylenes; and the like. Preferred R groups include:2,2-bis(p-hydroxyphenyl) propane, methylene and 2-hydroxypropylene.

In Formula VI, each z is individually a functional group which isreactive with the hydrolyzed nitrogen of the partially hydrolyzed,poly(N-acyl alkylenimine). Suitable z groups include, but are notlimited to: halides such as chloride, bromide and the like; isocyanates;epoxides; aldehydes; carboxylic groups; hydroxy or alkoxy methyl groups;other known groups reactive with amines; and suitable mixtures thereof.

Suitable crosslinkers include, but are not limited to: dicarboxylicacids such as malonic, phthalic and oxalic; epichlorohydrin;dihaloalkanols such as dichloropropanol; methylene bis formamide;bisisocyanates such as m-tolylene diisocyanate, isophorone diisocyanate;aldehydes such as formaldehyde, glutaraldehyde; diepoxides such asbutadiene diepoxide, diglycidyl ether of Bisphenol-A; other knowncrosslinkers; and mixtures thereof. Typical crosslinkers include thosecrosslinking agents disclosed in U.S. Pat. No. 3,640,909 (Jones et al.).

Crosslinked, partially hydrolyzed, poly(n-acyl alkylenimine) derivativeswill contain from 1 up to m-1 R₃ groups, as defined previously, andcontain repeating units represented by the structural formula: ##STR7##wherein: a, Q, R₁, R₂, v, x, y and z are as previously defined inFormula IV and m' is from 2 to m as previously defined in Formula VI.The crosslinking group, defined by R₄ in Formula VII, is a polyvalenthydrocarbyl-containing group which is the residue of the crosslinker ofFormula VI.

The amount of derivatizing agent provided is not critical but will varydepending upon the desired extent of derivatization. Typically, theamount of derivatizing agent will be from about 0.01 to about 10,preferably from about 0.5 to about 6, and most preferably from about0.01 to about 1 moles per mole of hydrolyzed nitrogen in the poly(N-acylalkylenimine).

The molecular weight of the partially hydrolyzed, poly(N-acylalkylenimine) of Formula III, or derivatives thereof of Formula IV, isnot critical by depends on the molecular weight of the poly(N-anylalkylenimine) precursor, the extent of partial hydrolysis, as well asthe degree and type of any derivatization. Generally, the partiallyhydrolyzed, poly(N-acyl alkylenimines), or derivatives thereof, of thisinvention will have a weight average molecular weight of at least about10,000, preferably from about 30,000 to about 20,000,000, and mostpreferably from about 150,000 to about 1,500,000.

In a typical embodiment, the derivatization procedure involves:providing either in-situ generation of partially hydrolyzed, poly(N-acylalkylenimine) or dissolution of pre-purified partially hydrolyzed,poly(N-acyl alkylenimine) at the desired concentration in the reactionsolvent; adding the derivatizing agent; adjusting the reaction pH toabout 10; and heating to reaction temperature of 60°-80° C. for a periodof about 5 hours, to obtain the derivatized, partially hydrolyzed,poly(N-acyl alkylenimine) in solution.

Particular preferred partially hydrolyzed, poly(N-acyl alkylenimines),and derivatives thereof, provided by poly(N-acyl alkylenimine)precursors of Formula I when R is ethyl and z is 2, contain repeatingunits represented by the structural formula: ##STR8## wherein a, Q, R₂,R₃, v, y and z are as defined in Formulas III or IV previously.

The personal care compositions of this invention comprise, andpreferably consist essentially of, carrier, an effective managing amountof partially hydrolyzed, poly(N-acyl alkylenimine), and optionallyeffective amounts of other personal care ingredients.

Carrier, including mixtures of carriers, used in the personal carecompositions of this invention act as a fluid vehicle for the partiallyhydrolyzed, poly(N-acyl alkylenimine) or derivative thereof, and otheroptional personal care ingredients. Such carriers may be any carrierselected from those well established in the personal care art.Illustrative examples of carriers include, but are not limited to:water, such as deionized or distilled water; alcohols, such as ethanol,isopropanol or the like; glycols, such as propylene glycol, glycerine orthe like; and mixtures thereof. Preferred carrier systems includeoil-in-water emulsions, water, ethanol and aqueous ethanol mixtures.

When the carrier is an aqueous solution, the pH may be varied over awide range depending upon the particular personal care application,based on those procedures well established in the art. Under acidic andneutral conditions, the partially hydrolyzed, poly(N-acyl alkylenimine)or derivative thereof may be provided predominantly in the quaternaryammonium form; whereas under basic conditions the partially hydrolyzed,poly(N-acyl alkylenimine) or derivative thereof may be providedpredominantly or essentially in the free amine form.

The amount of poly(N-acyl alkylenimine) polymer provided in the personalcare composition of this invention is an effective managing amount,which is defined as that amount of polymer sufficient to provideeffective or improved personal care utility to the composition.

In quantitative terms, the effective managing amount of polymer willvary depending upon the particular personal care application and extentof managing properties desired. In general, an effective managing amountof polymer will range between about 0.01 and about 25, preferably fromabout 0.1 to about 5, and most preferably from about 0.25 to about 2.5,weight percent of the total weight of the personal care composition.

The personal care compositions of this invention may optionally containsuitable ingredients or additives typical of personal care compositions,following well established practices in the art. Illustrativeingredients which may be suitable may include, but are not limited to,the following, including mixtures thereof. Illustrative surfactants mayinclude: anionics such as fatty acid soaps, alkyl sulfates, alkyl ethersulfates, alkyl aryl sulfonates, sarcosinates and preferably sodiumlauryl sulfate, ammonium lauryl sulfate, triethanol amine laurylsulfate, sodium laureth sulfate, triethanol amine stearate and glycerolmonostearate; nonionics such as fatty acid alkanol amides, alkyl arylpolyglycol ether, polyglycol ethers and preferably cocamide DEA,nonoxynol-7 and octoxynol-9; cationics such as alkyl trimethyl ammoniumsalts, quaternized amides of ethylene diamine, alkyl pyridinium saltsand preferably cetrimonium chloride, stearalkonium chloride and cetylpyridinium chloride; and amphoterics such as alkyl o-aminopropionates,betaines, alkyl imidazolines and preferably cocamidopropyl betaine andcaproamphocarboxypropionate. Illustrative cleansers may includee naturaloils and alcohols and preferably mineral oil, lanolin oil, ethanol andisopropanol. Illustrative colorants may include pigments, dyes, andpreferably FD&C Blue No. 1, FD&C No. 1 Aluminum Lake or similar sets ofgreen, red or yellow. Illustrative preservatives may include alcohols,aldehydes, p-hydroxybenzoates and preferably methylparaben,propylparaben, glutaraldehyde and ethyl alcohol. Illustrativemoisturizers may include fatty alcohols, fatty esters, glycols andperferably isopropyl myristate, lanolin or cetyl alcohols, propylenegylcol, glycerol and sorbitol. Illustrative pH adjustors may includeinorganic and organic acids and bases and preferably aqueous ammonia,citric acid, phosphoric acid, acetic acid, triethanolamine and sodiumhydroxide. Illustrative emulsifiers may include anionic and nonionicsurfactants and preferably stearic acid, glycerol monostearate, cocoyldiethanolamide, and the preferred anionic and nonionic surfactantslisted previously. Illustrative propellants may include hydrocarbons,fluorocarbons, ethers, carbon dioxide, nitrogent and dimethyl ether.Illustrative reducing agents may include ammonium thioglycolate andsodium thioglycolate. Illustrative conditioners may include homo- andcopolymers of dialkyldimethyl ammonium chloride and acrylamide,copolymers of quaternized dimethyl aminoethyl acrylate and methacrylatewith vinyl pyrrolidone and acrylamide, quaternary nitrogen-containingcellulose ethers, and preferably polyquaternium-10, polyquaternium-6 andpolyquaternium-11. Illustrative thickeners may include sodium chloride,hydroxyethyl cellulose hydroxypropyl methyl cellulose, sodiumcarboxymethyl cellulose, guar gum and derivatives thereof, xanthan gumand derivatives thereof and polymers containing hydrophobe bunchesincluding hydrophobe modified polyurethanes or other such polymersdescribed in U.S. Pat. No. 4,426,485.

Other typical ingredients may include, but are not limited to, thefollowing: fragrances; foaming agents; sunscreen and suntan agents;depilatory agents; flavors; astringent agents; antiseptics; deodorants;antiperspirants; insect repellants; bleaches and lighteners;anti-dandruff agents; adhesives; polishes; strengtheners for hair,nails, or the like; fillers; barrier materials; and other known personalcare additives. Mixtures of such ingredients may also be provided.

The amount of ingredient contained in the personal care compositions ofthis invention is not critical but will vary depending upon theparticular ingredient, composition and desired use level and can be anyeffective amount for achieving the desired property provided by suchingredients, following well established procedures known to those in thepersonal care art.

The personal care compositions of this invention are produced byproviding an effective managing amount of partially hydrolyzed,poly(N-acyl alkylenimine), or derivatives thereof, along with optionalpersonal care additives, such as any one or more of the ingredientspreviously described, to a suitable carrier. Typically, the polymer andother personal care additives may be admixed in the carrier to provide apersonal care composition, following well established procedures.

The personal care compositions of this invention are used by applying aneffective managing amount of the personal care composition to the hair,skin, teeth or other similar personal care substrate following thosetechniques well established in the personal care art. In a preferredembodiment, a process for managing keratinous substrates, such as hairor skin, is provided by applying an effective managing amount ofpersonal care composition containing partially hydrolyzed, poly(N-acylalkylenimine) to the keratinous substrate.

Illustrative personal care uses of this invention include, but are notlimited to, the following: skin creams including cleansing, night,massage, moisturizing, vanishing, foundation, hand, hand/and-body,all-purpose creams and other known skin creams; astringents and skintonics, including compositions for irritated, inflamed, allergic,hypersensitive or sensitized skin; protective creams and hand cleansers;bath preparations including foam baths, bath salts, bath oils,after-bath products, and other known bath preparations; baby skin andhair products; adolescent skin products, such as for oily skin or acne,and other adolescent skin products; antiperspirants and deodorants;depilatories; shaving preparations including wet shaving creams, sticks,foams, dry shaving lotions, powder, after-shave lotions, foams,aerosols, gels, creams, balms and powders, and other known shavingpreparations; foot preparations including foot powders, sprays, creams,corn, callus and chilblain and athelete's foot preparations and otherknown foot preparations; insect repellants; sunscreen, suntan andanti-sunburn preparation; skin lighteners or bleaches; face packs ormasks including wax-, rubber-, vinyl-, hydrocolloid- or earth-basedsystems, anti-wrinkle preparations and other known face packs or masks;perfumes; face powders and make-up; colored make-up preparationsincluding lipstick, lip salves, rouge, eye make-up such as mascara, eyeshadow, eye liner and other known make-up preparation; shampoosincluding clear liquids, liquid creams or lotions, solid creams or gels,oils, powders, aerosols, dry, conditioning, baby, anti-dnadruff andmedicated, acid-balanced shampoos and other known shampoos; hair settingpreparations including lotions, sprays, dressings, brilliantines,fixatives, aerosols, emulsions, gels, and other known hair preparations;hair tonics and conditioners including rinses; hair colorants includingtemporary, semi-permanent, permanent or other hair dyes or colorants,hair dye removers, bleaches, lighteners and other known hair colorants;permanent wave and hair strengtheners; hair straighteners includingcaustic preparations, chemical hair reducing preparations and otherknown hair straighteners; dental products including dentifrices such astooth paste, tooth gels, tooth powders, solid dentifrice, denturecleansers, adhesives, and other known dental products; mouth washes; andother known personal care compositions.

The novel, partially hydrolyzed, poly(n-acyl alkylenimines), andderivatives thereof, of this invention may be useful in applicationsother than personal care, such as flocculants, additives in papermanufacture, or other areas which known poly(N-acyl alkylanimines)provide utility.

The following examples are presented as illustrative embodiments of thisinvention and are not included to limit the scope thereof. Unless statedotherwise all percentages are given in weight percent.

EXAMPLES

The various designations used in the examples are defined as follows:

    ______________________________________                                        Designation Description                                                       ______________________________________                                        SB-85       An aqueous solution of stearalkonium                                          chloride, at 85 wt. % active                                                  concentration, identified as                                                  BARQUAT ® SB-85 by Lonza, Inc.                                CHPDLACl    3-chloro-2-hydroxypropyldimethyl-                                             lauryl ammonium chloride.                                         CHPTACl     3-chloro-2-hydroxypropyltrimethyl                                             ammonium chloride.                                                EDTA        Trisodium salt of                                                             ethylenediaminetetraacetic acid.                                  EPTACl      2,3-epoxypropyltrimethyl ammonium                                             chloride.                                                         ES-225      A half ethyl ester of maleic                                                  anhydride/vinyl methyl ether                                                  copolymer, identified as                                                      GANTREZ ® ES-225 by GAF Corp.                                 GAF 937     A copolymer of vinyl pyrrolidene and                                          dimethyl aminoethyl methacrylate,                                             identified as GAF ® 937 by GAF Corp.                          HEC         A hydroxyethyl cellulose having a                                             degree of substitution of about 2.0.                              H.sub.MW QNHEC                                                                            Quaternary-nitrogen containing                                                hydroxyethyl cellulose derivatized                                            with 3-chloro-2-hydroxypropyltri-                                             methyl ammonium chloride, having a 2                                          wt. % Brookfield viscosity of 456 cps                                         and about 1.8 wt. % nitrogen.                                     L.sub.MW QNHEC                                                                            Quaternary-nitrogen containing                                                hydroxyethyl cellulose derivatized                                            with 3-chloro-2-hydroxypropyltri-                                             methyl ammonium chloride, having a 2                                          wt. % Brookfield viscosity of 125 cps                                         and about 1.8 wt. % nitrogen.                                     MCHS        Monochlorohydrin sulfonate.                                       PEG-60 Lanolin                                                                            A 60 mole ethoxylate of lanolin,                                              identified as Solan ®  brand by                                           Croda.                                                            PPEI(20M)   Homopolymer of N--propionyl                                                   ethylenimine having a weight average                                          molecular weight of 20,000,                                                   identified as Poly(ethyloxazoline)                                            XAS-10874.01 by Dow Chemical Co.                                  PPEI(200M)  Homopolymer of N--propionyl                                                   ethylenimine having a weight average                                          molecular weight of 200,000,                                                  identified as Poly(ethyloxazoline)                                            XAS-10874.03 by Dow Chemical Co.                                  PPEI(500M)  Homopolymer of N--propionyl                                                   ethylenimine having a weight average                                          molecular weight of 500,000,                                                  identified as Poly(ethyloxazoline)                                            XAS-10874.05 by Dow Chemical Co.                                  RH          Relative humidity.                                                ES-2        A sodium laureth sulfate, identified                                          as STANDAPOL ® ES-2 by Henkel Corp.                           STEARETH-20 A polyethylene glycol ether of                                                stearyl alcohol, identified as                                    20 by ICI Americas.H ®                                                    TEALS       Triethanolamine lauryl sulfate.                                   TWEEN ® 20                                                                            A polysorbate mixture of laurate                                              esters, identified as TWEEN ® 20 by                                       ICI Americas.                                                     ______________________________________                                    

Polymer Characterization Procedures

Unless otherwise indicated, the following test procedures for polymercharacterization are used in the examples.

Ash Analysis: The average weight percent of component is determined byelemental analysis using standard ashing procedures measured relative tothe dry polymer.

DS: The degree of substitution is the average mole percent of thesubstituted nitrogen determined by the numerical average of the molepercent values using the following three procedures:

Potentiometric Titration; the average mole percent hydrolysis, based onmillipores of propionic acid, is determined analytically by standardtitration procedures, factoring out the contribution of aminehydrochloride substitution.

Chloride content, % Cl; the average weight percent of chloride isdetermined analytically using standard Ash Analysis procedures asdescribed previously.

Nitrogen content, % N; the average weight percent of nitrogen isdetermined analytically by standard Kjeldahl procedures.

Viscosity: viscosity is measured using Brookfield LVT viscometers, basedon an aqueous solution of 2 wt. % designated polymer at 25° C.

Performance Testing Procedures

Unless otherwise indicate, the following testing procedures are used tomeasure various properties of the poly(N-acyl alkylenimines) which aresignificant in indicating personal care utility. Where specified,treated hair tresses are provided using a two gram, 10-inch tress ofcommercially available virgin brown hair. One milliliter of a 1 wt. %solution of designated polymer in water solvent, with or withoutsurfactant is applied to the tress manually.

Appearance: Hair treated with poly(N-acyl alkylenimines) is rated on ascale of from 1 to 5, with 5 as the highest rating, with respect to wetand dry sheen, dry flakiness and other known appearance properties.

Combability: Wet and dry combability is measured by combing a treatedhair tress and measuring how far the comb travels before it is stoppedby tangles. Tresses which are 10 inches in length, i.e., 23 centimeters,provide a maximum value of 23.

Curl Retention: This test measures the ability of the poly(N-acylakylenimines) to hold a hair sample in a curl after the polymer isapplied and the curl rolled. The test measures the rate and extent ofrelaxation of a curl formed by a hair roller as follows. The polymer isapplied manually and not by spray to facilitate a more uniformapplication of the polymer to the hair. The test is conducted underconstant temperature and humidity conditions and measures the loss ofcurl over time. The treated hair tresses are wound around and clipped toa 2 by 7 centimeter roller, with commercial end paper. The rolled tressis dried for about an hour and then brought to the constant temperatureand humidity test conditions over about an hour. The tress is slidgently from the roller, the end paper is removed and the horizontallength of the curl measured. The test is begun by hanging the curl inair and continues by monitoring the change in the length over time.Mesurements are taken at 15 minute intervals for 1 hour. Data isrecorded as percent curl retention, calculated from the followingrelationship: ##EQU1## wherein: L_(I) is the initial length of thetress;

L_(C) is the initial length of the curl; and

L_(T) is the length of the curl at specified time.

The rate of loss of curl retention is obtained using linear regressionanalysis of the linear equation obtained by plotting the naturallogarithm of curl retention as a function of time.

Feel: Hair tresses, produced as described in the Examples, areevaluated, on a scale of 1 to 5 with 5 as the highest rating, withrespect to greasiness, stickiness, dryness, softness, slip and otherstandard performance properties.

Fly-away: This test measures the diameter of the hair tress afterrapidly combing the tress 10 times. Superior performance is provided bylower values.

Gloss: This test measures the glossiness, using a Gardiner glossimeterat ambient conditions, of films of the specified polymer cast on thebottom of wax coated cups, at 20° and 60° angles of incidence.

Moisture Retention: This test measures the ability of polymer to retainwater, providing an indication of humectancy in personal care. The testprocedure involves dessicating polymer in a vacuum oven at approximately50° C. The dried polymer is placed in an enclosed chamber over asaturated salt solution and the amount of water uptake in the polymer ismeasured, based on increased weight. The percent moisture obtained at aspecified relative humidity is measured after exposure at ambienttemperature for 138 hours.

Solubility: Specified weight percent solutions of designated poly(N-acylalkylenimines) in various solvents are measured with respect tosolubility of the polymer in such solutions.

Sprayability: This test measures the ability of the specified solutionof designated poly(N-acyl alkylenimines) to provide a spray, using apump or aerosol procedure. Sample mists are measured, on a scale of 1 to10 with 10 as the highest rating, with respect to spray pattern,fineness of spray, area coverage, drying rate and droplet formationcharacteristics.

Viscosity Stability: This test measures the storage stability ofdesignated poly(N-acyl alkylenimines) solutions to retain viscosity intime. The specified weight percent polymer solutions are produced andstored for three months. The viscosity of such solutions is measured, atspecified times, using the previously described procedure.

EXAMPLES 1-15: Partial Hydrolysis of Poly(N-acyl alkylenimines)

These Examples illustrate various procedures for preparing andrecovering partially hydrolyzed, poly(N-acyl alkylenimines) used in thisinvention.

EXAMPLE 1

A 2-liter reaction flask is equipped with a mechanical stirrer, refluxcondenser, thermometer, dropping funnel, and oil bath with automaticcontrol. Deionized water, 912 g, is added and 96 g of PPEI (200M) isadded in one portion and stirred until dissolved. The reactor is closedand heated to reflux in 58 minutes; the polymer clouds out of solutionabove about 75° C. Concentrated HCl, 48.5 g, is added from the droppingfunnel in 20 seconds, and the reflux is continued for 90 minutes; thepolymer dissolves in the reaction medium at about 40-50 minutes. Thereaction is cooled to 28° C. in 12 minutes and a sample is pulled foranalysis of the degree of hydrolysis by gas chromatography. The reactionmedium is neutralized to pH 6.6 with 20.5 weight percent NaOH, the wateris removed under a vacuum, the solids are dissolved in anhydrousethanol, the solution is filtered, the ethanol is removed under vacuum,and the solid product is dried in a 50° C. vacuum oven for 48 hours.Product analysis is set forth in Table I.

EXAMPLE 2

The procedure in Example 1 is repeated except the PPEI(200M) is replacedwith 96 g of PPEI(20M). Product analysis is set forth in Table I.

EXAMPLE 3

The procedure in Example 1 is repeated except that the PPEI(200M) isreplaced with 96 g of PPEI(500M). Product analysis is set forth in TableI.

EXAMPLE 4

A 2-liter reaction flask is equipped with a mechanical stirrer, refluxcondenser, thermometer, dropping funnel, and oil bath with automaticcontrol. Distilled water, 912 g, is added and 96 g of PPEI(200M) addedin one portion and stirred until dissolved. The reactor is closed andheated to reflux in 50 minutes; the polymer clouds out of solution above76°. Concentrated HCl, 48.5 g, is added in 45 seconds and reflux iscontinued for 90 minutes; the polymer dissolves in the reaction mediumat about 40 minutes. The reaction is cooled to 28° C. in 10 minutes anda sample is taken for hydrolysis analysis. The solution is treated withenough Amberlite®900 resin in the hydroxide form to a pH of 11.5, theresin is filtered, and the product is isolated by roto-evaporation andfreeze drying. Product analysis is set forth in Table I.

EXAMPLE 5

A stirred Parr reactor, Model 4522 made of monel alloy, is equipped witha dip tube, cooling coils, nitrogen source, and sampling cylinder.PPEI(200M), 95 g, is predissolved in 938.3 g of distilled water andtransferred to the reactor. Concentrated HCl, 11.72 g, is added withswirling, the reactor is sealed, and the stirrer motor and coolant isstarted. The reactor is heated to 120° C. in 25 minutes and 45 psig isgenerated. Samples are pulled for hydrolysis analysis via the samplingcylinder at one hour intervals. The reactor is rapidly cooled after 5.92hours reaction, opened, and 20.9 g of 20.07% sodium hydroxide is addedto adjust the solution pH to 6.87. The product is isolated byroto-evaporation and freeze drying to give a crisp, greenish-coloredsolid. The green color comes from Cu and Ni salts due to corrosion ofthe Monel stirrer. Product analysis is set forth in Table I.

EXAMPLE 6

A 250 ml 3-necked flask is equipped with a mechanical teflon stirrer,thermometer, condenser, oil bath, and dropping funnel. Anhydrous 2Bethanol, 105.4 g, is charged and 12 g PPEI(200M) is dissolved withstirring. The solution is heated to reflux (80° C.) in 45 minutes and14.6 g of concentrated HCl is added in 20 seconds. The reaction isallowed to continue for 2 hours and quickly cooled to ambient, and asample is taken for hydrolysis analysis. The mixture is treated with20.07% sodium hydroxide to a pH of 6.8. The product is isolated byroto-evaporation and analyzed with the results set forth in Table I.

EXAMPLE 7

The same reaction apparatus as described in Example 1 is used. Deionizedwater, 1672 g, is added and 169.5 g of PPEI (200M) is added over severalminutes and dissolved with stirring. The reactor is closed and heated toreflux in 30 minutes; the polymer clouds out of solution above about 75°C. Concentrated HCl, 20.8 g, is added from the dropping funnel andreflux is maintained for a total of 17 hours, at which time the polymeris dissolved in the reaction medium. The reaction is cooled to 25° C. in30 minutes and a sample is pulled for analysis of degree of hydrolysisby gas chromatography. The reaction medium is neutralized to pH of 6.8by the addition of 47.9 g of 20.07 weight percent NaOH. The solidpolymer is isolated by roto-evaporation and freeze drying. Productanalysis is set forth in Table I.

EXAMPLE 8

The procedure in Example 7 is repeated except the hydrolysis is done foronly 16 hours. Product analysis is set forth in Table I.

EXAMPLE 9

The procedure is Example 8 is repeated except the PPEI (200M) isreplaced with 169.5 g of PPEI (500M). Product analysis is set forth inTable I.

EXAMPLE 10

The procedure in Example 8 is repeated except the reaction medium isoverneutralized to pH 7.9 with 17.5 g of 50 weight percent NaOH andback-neutralized to pH 7.02 with concentrated HCl. The isolated producthad a high salt content which was reduced by dissolving the solids in90/10 w/w acetone/water at a 10 weight percent concentration, filtering,and removal of the ethanol by roto-evaporation. The residue wasredissolved in water and freeze dried. Product analysis is set forth inTable I.

EXAMPLE 11

A 500 ml reaction flask is equipped with a mechanical stirrer, refluxcondenser, thermometer, dropping funnel, and an oil bath with automaticcontrol. Deionized water, 418 g, is added and 42.4 g of PPEI (200M) isadded in one portion and dissolved with stirring. The reactor is closedand heated to reflux in 45 minutes. Concentrated HCl, 5.2 g, is addedand the reflux is maintained for 16 hours. The reaction temperature ismaintained between 95° C. and 98° C., while 19.95 g of 20.07 weightpercent NaOH is slowly added to bring the reaction medium to pH 10.63;polymer begins clouding out at about 6.5 pH and is in solid form at thefinal pH. The liquid phase was removed with suction through a submergedfilter. The concentrated polymer phase is cooled to ambient temperatureto give a concentrated solution of product. Both the liquid effluent andthe concentrated polymer solution are freeze dried to isolate solids.Product analysis is set forth in Table I.

EXAMPLE 12

The procedure in Example 11 is repeated except that the amount ofdeionized water is reduced to 401 g, the amount of concentrated HCl isincreased to 21.3 g, and the hydrolysis reaction time is decreased to 90minutes. A total of 63.15 g of 20.07 weight percent NaOH is added atabout 98° C. to adjust the reaction pH to 11.05 and the liquid phase isremoved by a submerged filter. Product analysis is set forth in Table I.

EXAMPLE 13

The procedure in Example 11 is repeated except that the amount ofdeionized water is reduced to 409 g, the amount of concentrated HCl isincreased to 13.0 g, and the hydrolysis reaction time is decreased to230 minutes. A total of 38.3 g of 20.07 weight percent NaOH is added atabout 96°-98° C. to adjust the reaction pH to 10.50 and the liquid phaseis removed by a submerged filter. Product analysis is set forth in TableI.

EXAMPLE 14

The procedure in Example 11 is repeated except that the amount of PPEI(200M) is increased to 92.84 g, the amount of deionized water decreasedto 343 g, the amount of concentrated HCl is increased to 28.52 g, andthe hydrolysis reaction time is decreased to 3 hours. A total of 101.2 gof 19.67 weight percent NaOH is added at about 97° C. to adjust thereaction pH to 10.7 and the liquid phase is removed by a submergedfilter. Product analysis is set forth in Table I.

EXAMPLE 15

The procedure in Example 14 is repeated except that the PPEI (200M) isreplaced with 92.84 g of PPEI (500M). Product analysis is set forth inTable I.

                  TABLE 1                                                         ______________________________________                                        PREPARATION OF PARTIALLY HYDROLYZED,                                          POLY(N--ACYL ALKYLENIMINES)                                                   Poly(N--acyl                                                                  alkylenimine)                    Salt                                                Molecular          Reactant                                                                             Degree of                                                                             Level                                       Weight    Concen-  Mole   Hydrolysis                                                                            (calc                                Example                                                                              (× 1000)                                                                          tration  Ratio.sup.a                                                                          (mole %).sup.b                                                                        wt. %).sup.c                         ______________________________________                                         1     200       9.1      0.495  11.6    3.95                                  2      20       9.1      0.495  11.3    7.52                                  3     500       9.1      0.495  13.2    2.55                                  4     200       9.1      0.495  13.0    3.10                                  5     200       9.1      0.12   11.0    7.37                                  6.sup.d                                                                             200       9.1      1.19    2.3    13.29                                 7     200       9.1      0.12   11.5    7.24                                  8     200       9.1      0.12   12.1    7.20                                  9     500       9.1      0.12   12.5    7.65                                 10     200       9.1      0.12   13.0    6.83                                 11     200       9.1      0.12   ND.sup.e                                                                              1.99                                 12     200       9.1      0.50   ND.sup.e                                                                              3.55                                 13     200       20.0     0.30   11.3    3.07                                 14     200       20.0     0.30   13.0    9.07                                 15     500       20.0     0.30   ND.sup.e                                                                              9.31                                 ______________________________________                                         .sup.a Moles of hydrolyzing agent per mole of poly(N--acyl alkylenimine)      repeat units.                                                                 .sup.b Moles of hydrolyzed nitrogen measured per mole of nitrogen in          poly(N--acyl alkylenimine), designated by parameter a in Formulas I and       IV, times 100. Determined by gas chromatography, based on equivalent mole     of propionic acid measured after hydrolysis.                                  .sup.c Calculated from average weight percent of sodium chloride using        previously described Ash Analysts procedure.                                  .sup.d Using anhydrous ethanol as diluent, instead of water.                  .sup.e Not determined.                                                   

EXAMPLES 16-26: Preparation of Nitrogen-Substituted Derivatives ofPartially Hydrolyzed, Poly(N-acyl Alkylenimines).

These examples illustrate procedures for preparing nitrogen-substitutedderivatives of partially hydrolyzed, poly(N-acyl alkylenimines) asprepared in the previous Examples 1-15. In Examples 16-19, thenitrogen-substituent contains a cationic group providing a dicationic,nitrogen-substituted derivative of partially hydrolyzed, poly(N-acylalkylenimine). In Examples 20-22, the nitrogen-substituent containshydrophobic, cationic groups providing a hydrophobic, dicationic,nitrogen-substituted derivative of partially hydrolyzed, poly(N-acylalkylenimine). In Examples 23 and 24, the nitrogen-substituent containsan anionic group providing an amphoteric, nitrogen-substituentderivative of partially hydrolyzed, poly(N-acyl alkylenimine). InExamples 25 and 26, the nitrogen-substituent contains a dihydroxy groupproviding a vicinal diol-containing, nitrogen-substituted derivative ofpartially hydrolyzed, poly(N-acyl alkylenimine).

EXAMPLE 16

A suitably sized 3-neck reaction flask is equipped with a mechanicalstirrer, pH probe, and an oil bath with automatic control. Deionizedwater, 34.5 g, is added and 15.75 g of the polymer produced in Example 4is added and dissolved with stirring. A 60 weight percent aqueoussolution of 3-chloro-2-hydroxypropyltrimethylammonium chloride, 6.39 g,is added and the pH is adjusted to 12.05 with 4.6 g of 20.26 weightpercent NaOH. The mixture is heated to 65° C. for 310 minutes whileadding small increments of the aqueous NaOH (an additional 0.2 g) tomaintain the pH at about 10.5. The reaction is cooled and neutralized toa pH of 6.85 with concentrated HCl. After freeze drying and initialanalysis, the product was dissolved in deionized water at a 10%concentration, dialyzed to remove impurities, and freeze dried. Productanalysis is set forth in Table II.

EXAMPLE 17

The procedure in Example 16 is repeated except that the amount ofdeionized water is 75 g, the polymer of Example 4 is replaced with 18.71g of the polymer prepared in Example 7, and 12.78 g of the 60%3-chloro-2-hydroxypropyltrimethylammonium chloride is added. A total of11.9 g of 20.07 weight percent NaOH is added to maintain the reactionpH. The reaction medium was purified by dialysis and the productisolated by freeze drying. Product analysis is set forth in Table II.

EXAMPLE 18

The procedure in Example 17 is repeated except the polymer of Example 7is replaced with 17.93 g of the polymer prepared in Example 9. A totalof 11.5 g of 20.07 weight percent NaOH is added to maintain the reactionpH. Product analysis is set forth in Table II.

EXAMPLE 19

A suitably sized 3-neck flask is equipped with a mechanical stirrer, apH probe, and an oil bath with automatic control. Deionized water isadded and 18.56 g of the polymer prepared in Example 7 is added anddissolved with stirring. A 70.54 weight percent aqueous solution of2,3epoxypropyltrimethylammonium chloride, 4.3 g, is added and the pH isadjusted to 11.7 with 3.0 g of 20.07 weight percent NaOH. The reactionis heated to 65° C. and held for 300 minutes while maintaining thereaction pH at about 10.5 with an additional 0.1 g of the 20.07 weightpercent NaOH. The reaction is cooled and the product purified bydialysis and freeze drying. Product analysis is set forth in Table II.

EXAMPLE 20

In the standard apparatus as in Example 19, 59 g of deionized water isadded and 18.71 g of the polymer prepared in Example 7 is added anddissolved with stirring. A 42.97 weight percent aqueous solution of3-chloro-2-hydroxypropyldimethyllaurylammonium chloride, 31.84 g, isadded and the pH is adjusted to 10.6 with 10.2 g of 20.07 weight percentNaOH. The reaction is heated to 65° C. and held for 300 minutes; pH iskept at about 10.5 with an additional 1.0 g of the aqueous NaOH. Thereaction is cooled and the somewhat viscous solution is diluted with 312g deionized water and decanted. The residue is diluted with 300 gdeionized water, centrifuged and decanted, dissolved in water, dialyzed,and freeze dried. Product analysis is set forth in Table II.

EXAMPLE 21

In the standard apparatus as in Example 19, 59 g of anhydrous 28 ethanolis added and 18.71 g of the polymer prepared as in Example 7 is addedand dissolved with stirring. A 42.97 weight percent aqueous solution of3-chloro-2-hydroxypropyldi -methyllaurylammonium chloride, 31.84 g, isadded and the pH adjusted to 10.83 with 9.8 g of 20.07 weight percentNaOH. The reaction is heated to 80° C. for 300 minutes while maintainingthe reaction pH with incremental additions of another 1.4 g of theaqueous NaOH. The reaction is cooled and the product is purified bydialysis and freeze drying. Product analysis is set forth in Table II.

EXAMPLE 22

The procedure in Example 11 is repeated except that the polymer ofExample 7 is replaced with 17.93 g of the polymer prepared in Example 9.A total of 10.9 g of 20.07 weight percent NaOH is added to adjust andmaintain the reaction pH. Product analysis is set forth in Table II.

EXAMPLE 23

In the standard apparatus as in Example 19, 25 g of deionized water isadded and 16.8 g of the polymer prepared in Example 8 is added anddissolved with stirring. A 30 weight percent aqueous solution ofmonochlorohydrinsulfonate, 11.8 g, is added and the pH, is adjusted to10.68 with 6.2 g of 20.07 weight percent NaOH. The reaction is heated to65° C. for 300 minutes with no adjustment needed to maintain the pH. Thereaction is cooled and the product is purified by dialysis and freezedrying. Product analysis is set forth in Table II.

EXAMPLE 24

The procedure in Example 23 is repeated except that the amount ofdeionized water is reduced to 67 g and the amount of 30 weight percentmonochlorohydrinsulfonate is increased to 23.6 g. Addition of 9.8 g of20.07 weight percent NaOH adjusts the reaction pH to 10.09. Productanalysis is set forth in Table II.

EXAMPLE 25

Nitrogen substitution of the partially hydrolyzed, poly(N-acylalkylenimine) produced in Example 10 is provided using the followingprocedure. In the standard apparatus as in Example 19, 150 g deionizedwater is added and 32.5 g of the polymer prepared in Example 10 is addedand dissolved with stirring. Glycidol, 5.82 g, is added and the pH isadjusted to 10.6 with 6.8 g of 19.60 weight percent NaOH. The reactionis heated to 65° C. for 300 minutes, cooled, and the product purified bydialysis and freeze drying. Product analysis is set forth in Table II.

EXAMPLE 26

The procedure is Example 25 is repeated except the amount of glycidol isincreased to 11.64 g and 7.0 g of the aqueous NaOH is used to obtain areaction pH of 10.55. Product analysis is set forth in Table II.

                  TABLE 2                                                         ______________________________________                                        PREPARATION OF NITROGEN-SUBSTITUTED                                           DERIVATIVES OF PARTIALLY HYDROLYZED,                                          POLY(N--ACYL ALKYLENIMINES)                                                          Polymer  Derivi-    Reactant                                                  Example  tizing     Mole   DS.sup.b                                                                             Visco-                               Example                                                                              Number   Agent      Ratio.sup.a                                                                          (mole %)                                                                             sity                                 ______________________________________                                        16     4        CHPTACl    1.0    5.9    32                                   17     7        CHPTACl    2.0    5.6    39                                   18     9        CHPTACl    2.0    5.3    31                                   19     7        EPTACl     1.0    4.6    36                                   20     7        CHPDLACl   2.0    7.7    >2000                                21.sup.c                                                                             7        CHPDLACl   2.0    5.8    580                                  22.sup.c                                                                             9        CHPDLACl   2.0    4.6    981                                  23     8        MCHS       1.0    6.4.sup.d                                                                            32                                   24     8        MCHS       2.0    12.8.sup.d                                                                           32                                   25     10       Glycidol   2.0    9.6.sup.e                                                                            33                                   26     10       Glycidol   4.0    10.8.sup.e                                                                           31                                   ______________________________________                                         .sup.a Moles of derivatizing agent per mole of hydrolyzed nitrogen.           .sup.b Degree of Substitution, using previously described analysis            procedures.                                                                   .sup.c Using anhydrous ethanol as reaction medium, instead of water.          .sup.d Calculated from weight percent sodium using previously described       Ash Analysis procedure.                                                       .sup.e Based on values from Potentiometric Titration procedure only, as       previously described.                                                    

EXAMPLES 27-56 AND CONTROLS A-K: Personal Care Evaluations

These examples illustrate various personal care compositions havingpartially hydrolyzed, poly(N-acyl alkylenimines) of this invention. InExample 27, the solubilities of various partially hydrolyzed,poly(N-acyl alkylenimines), or nitrogen-substituted derivatives thereof,are evaluated. In Examples 28-32, personal care compositions containingthe designated concentrations of partially hydrolyzed, poly(N-acylalkylenimines) are prepared by mixing together the listed ingredients.In Examples 33-35 and Controls A-B, hair spray formulations containingvarious partially hydrolyzed, poly(N-acyl alkylenimines) are analyzedand compared to commercially available polymers. In Examples 36-43 andControls C-D the stability of various partially hydrolyzed, poly(N-acylalkylenimine) solutions and formulations are evaluated. In Examples44-48 and Controls E-H the film properties of various partiallyhydrolyzed, poly(N-acyl akylenimines) are analyzed and compared tocommercially available polymers. In Examples 49-51 and Controls I-J thehygroscopicity of various partially hydrolyzed, poly(N-acylalkylenimine) solutions and formulations is evaluated. In Examples 52-55and Control K the substantivity of various partially hydrolyzed,poly(N-acyl alkylenimines) is evaluated. In Example 56 the toxicity ofvarious partially hydrolyzed, poly(N-acyl alkylenimines) is evaluated.

EXAMPLE 27: Solubility Analysis

This example demonstrates that partially hydrolyzed, poly(N-acylalkylenimines), and nitrogen substituted derivatives thereof, aresoluble in a wide variety of solvents.

Partially hydrolyzed, poly(N-propionyl alkylenimines) produced inExamples 1-3 provide complete solubility at 5 and 10 weight percentconcentrations in propylene glycol and glycerin, as well as at 20 weightpercent in water and anhydrous ethanol. Nitrogen-substituted cationicderivatives of partially hydrolyzed, poly(N-propionyl alkylenimines)produced in Examples 16-22 provide solubility in acetone and chloroform.Nitrogen substituted, hydrophobe modified, cationic derivatives ofpartially hydrolyzed poly(N-propionyl alkylenimines), produced inExamples 20-22, provide complete solubility in ethanol, acetone andchloroform.

Partially hydrolyzed, poly(N-acyl alkylenimines) are also soluble inaqueous solutions over a wide range of temperatures and pH. Thepartially hydrolyzed, poly(N-propionyl alkylenimine) produced in Example4 is completely soluble at a pH of 1 up to 100° C., at a pH of 11.1 acloud point in aqueous solution at 72°-76° C. is provided; and at a pHof 10.8 in ethanol no cloud point is exhibited up to reflux temperatureof 80° C.

EXAMPLE 28: Hand Lotions

Hand lotions containing the designated concentrations ofpoly(N-propionyl ethylenimines), produced in Examples 9 and 10 areprepared by combining the ingredients listed below using the followingprocedure: Preparation procedure :

1. Heat the oil phase to 70° C.

2. In separate container, dissolve the polymer in water then add otherwater phase ingredients and heat to 70° C.

3. Add the water phase to the oil phase while stirring vigorously.

4. Continue stirring until the temperature of the lotion is 30°-35° C.

Oil phase:

    ______________________________________                                        Mineral Oil (carrier)                                                                              2.4                                                      Isopropyl myristate (emollient)                                                                    2.4                                                      Stearic acid (thickener)                                                                           2.9                                                      Lanolin alcohol (emulsifier)                                                                       0.5                                                      Cetyl alcohol (thickener/                                                                          0.4                                                      stabilizer)                                                                   Glycerol monostearate                                                                              1.0                                                      (thickener/stabilizer)                                                        Propyl paraben (preservative)                                                                      0.05                                                     ______________________________________                                    

Water phase:

    ______________________________________                                        Triethanolamine (pH adjustor)                                                                       0.95                                                    Propylene glycol (humectant)                                                                        4.8                                                     Methyl paraben (preservative)                                                                       0.1                                                     Polymer               0, 0.25, 0.4,                                                                 0.5, 1.0 and 2.0                                        Water (carrier)       to 100                                                  ______________________________________                                    

Although some incompatibility is exhibited, the hand lotion formulationscontaining 0.25 and 0.4 weight percent polymer are stable for prolongedperiods at ambient conditions. At 2 weight percent polymerconcentrations the hand lotion formulations are stable at ambienttemperature for several weeks. At 50° C. in an accelerated aging testanalysis for 28 days, the hand lotion formulations containing 0.25weight percent polymers are completely stable; at 0.4 weight percentpolymers a slight loss in homogeneity is exhibited; whereas at 0.5weight percent or higher polymer concentrations phase separation occursovernight.

EXAMPLE 29 PERMANENT WAVE FORMULATIONS

Permanent wave compositions containing the designated concentrations ofpoly(N-propionyl ethylenimines), produced in Examples 8, 9 and 10, areprepared by combining the following ingredients:

    ______________________________________                                        Ammonium thioglycolate  9.0                                                   (reducing agent)                                                              EDTA (metal chelating agent)                                                                          0.2                                                   Propylene glycol (humectant)                                                                          2.5                                                   Aqueous ammonia         to pH 9-9.2                                           (pH adjustor)                                                                 Polymer                 0, 1 and 2                                            Water (carrier)         to 100                                                ______________________________________                                    

EXAMPLE 30 AFTER SHAVE FORMULATIONS

After shave compositions containing the designated concentions ofpoly(N-propionyl ethylenimines), produced in Examples 8, 9 and 10,prepared by combining the following ingredients:

    ______________________________________                                        Propylene glycol (humectant)                                                                          0.5                                                   Polymer                 0, l and 2                                            Anhydrous ethanol (2B)  to 100                                                (carrier)                                                                     ______________________________________                                    

EXAMPLE 31 SHAMPOOS

Shampoos containing the designated concentrations of poly(N-propionylethylenimines), produced in Examples 9 and 10, are prepared by combiningthe following ingredients:

    ______________________________________                                        TEALS (40% active) (surfactant)                                                                        7.0                                                  Lauric diethanolamide    2.0                                                  (foam booster)                                                                TWEEN ® 20 (fragrance                                                                              3.0                                                  stabilizer and emollient))                                                    STANDAPOL ® ES-2 (surfactant)                                                                      5.0                                                  EDTA (metal chelating agent)                                                                           0.1                                                  Methyl paraben (preservative)                                                                          0.2                                                  Propyl paraben (preservative)                                                                          0.1                                                  Polymer                  0, l and 2                                           Water (carrier)          to 100                                               ______________________________________                                    

EXAMPLE 32 CONDITIONING CREMES

Conditioning creme rinse containing the designated concentrations ofpoly(N-propionyl ethylenimines), produced in Examples 9 and 10, areprepared by combining the ingredients listed below using the followingprocedures: Preparation Procedure:

1. Heat oil phase to 75° C.

2. Separately, dissolve polymer in available water and heat to 75° C.

3. Add oil phase to water phase while stirring vigorously.

4. Start cooling, continue stirring, and add ucarcide when temperatureis 35°-40° C.

5. Continue stirring until cooled to 30 ° C. Oil Phase:

    ______________________________________                                        Mineral oil (carrier)     2.0                                                 SB-85 (conditioner)       6.0                                                 Cetyl alcohol (thickener) 1.25                                                Glycerol monostearate (emulsifier)                                                                      0.75                                                ______________________________________                                         Water Phase:

    ______________________________________                                        UCARCIDE ® 225 biocide                                                                            0.4                                                   (preservative)                                                                Polymer                 0, l and 2                                            Water (carrier)         to 100                                                ______________________________________                                    

EXAMPLES 33-35 AND CONTROLS A AND B Hair Spray Analysis

Hair spray formulations containing 1.5 weight percent designatedpolymer, 49.25 weight percent deconized water and 49.25 weight percentethanol are evaluated using the previously described performance testingprocedures, with the results set forth in Table 3.

                  TABLE 3                                                         ______________________________________                                        HAIR SPRAY ANALYSIS DATA                                                                                       Control                                                                              Control                               Example:   33      34      35    A      B                                     ______________________________________                                        Polymer:   Ex. 1   Ex. 2   Ex. 3 H.sub.MW                                                                             ES-225                                                                 QNHEC                                        Wet Tests:                                                                    Combability                                                                              19      16      21    16     23                                    Feel       5       5       5     5       5                                    Appearance 5       5       5     4       5                                    Dry tests:                                                                    Combability                                                                              23      23      23    23     23                                    Fly-away   10.9    6.4     6.4   6.4      3.8                                 Appearance 4       5       5     5       5                                    Curl retention.sup.a :                                                        at 50% RH %                                                                              83      91      80    95     84                                    Rate of loss.sup.b                                                                       19      6       17    10     10                                    at 95% RH %                                                                              73      76      --    --     .sup. --.sup.c                        Rate of loss.sup.b                                                                       48      34      --    --     --                                    Sprayability:.sup.d                                                           Pattern    10      10      10    --     --                                    Wetness    10      10      10    --     --                                    ______________________________________                                         .sup.a at 70° F. and designated humidity                               .sup.bΔ Ln curl retention/minute × 10.sup.4                       .sup.c generally 60%                                                          .sup.d For a 2 wt. % polymer solution in ethanol using a commercially         available pump spray unit.                                               

Two weight percent solutions of various partially hydrolyzed,poly(N-acyl alkylenimines) in ethanol also exhibit good sprayabilityboth in terms of spray pattern, including fineness of spray and areacoverage, and quick drying performance, using pressurized aerosol sprayswith hydrocarbon propellant.

The partially hydrolyzed, poly(N-acyl alkylenimines) perform comparably,and in some respects including humidity resistance perform superior to,the commercial available control polymers.

EXAMPLE 36-43 AND CONTROLS C-D STABILITY ANALYSIS

Two weight percent aqueous solutions of the partially hydrolyzed,poly(N-propionyl ethylenimines) produced in Examples 1 and 3 areprepared and adjusted to a pH of 3.0 using sulfuric acid. Viscosities ofthe resulting solutions, following the previously described procedureusing a UL adaptor at 60 RPM, are measured at room temperature, of about25° C., and at 40° C. The resulting measurements, taken over severalweeks, are set forth in Table 4.

                  TABLE 4                                                         ______________________________________                                        VISCOSITY STABILITY AT LOW PH OF 3.0                                                           Viscosity (cps,)                                                     Temperature                                                                            over time, in weeks                                          Example   (°C.)                                                                             0       1   2     3   4                                  ______________________________________                                        36        25         6.1     6.4 6.1   6.2 6.0                                37        40         6.1     6.3 --.sup.a                                                                            5.7 5.4                                38        25         3.5     3.7 3.2   3.6 3.5                                39        40         3.5     3.3 3.2   3.2 3.2                                ______________________________________                                         .sup.a not available                                                     

The results indicate that at an acidic pH solutions of partiallyhydrolyzed, poly(N-acyl alkylenimines) exhibit good storage stability.In constrast, solutions of cationic cellulosic materials are subject toacid hydrolysis thereby providing poor stability at low pH. Thestability provided by partially hydrolyzed, poly(N-acyl alkylenimines)at acidic pH demonstrates the utility of such material in hair-careproducts, such as lower pH conditioners which impart better appearenceto the hair due to a natural ability to cause the cuticle in the keratinto lay down closer to the hair shaft, thereby producing a glossiersurface and resulting the increased hair manageability.

Stability at high pH is evaluated in cream formulations, specificallycalcium hydroxide cream relaxer products, using partially hydrolyzed,poly(N-propionyl ethylenimines) produced in the Examples 1 and 5, aswell as a control formulation of identical ingredients but withoutpolymer, as follows:

    ______________________________________                                        HIGH PH CREAM FORMULATIONS                                                                             Amount                                               Ingredient               (wt. %)                                              ______________________________________                                        Polymer                  2                                                    Propylene glycol (humectant)                                                                           5                                                    Petrolatum (texturizer)  12                                                   Mineral oil (carrier)    10                                                   Cetyl alcohol (thickener)                                                                              8                                                    Steareth-20 (emulsifier) 3                                                    PEG-60 lanolin (emulsifier)                                                                            1.5                                                  Calcium hydroxide (pH adjustor)                                                                        5.5                                                  Fragrance                0.25                                                 Water (carrier)          to 100                                               ______________________________________                                    

The storage stability of these formulations, at room temperature ofabout 25° C. and at 40° C., are evaluated by measuring viscosity,separation or preciptation with the results set forth in Table 5.

                                      TABLE 5                                     __________________________________________________________________________    STORAGE STABILITY AT HIGH PH                                                  (Ca(OH).sub.2 CREAM RELAXER)                                                                 Viscosity (10.sup.5 cps)                                               Temperature                                                                          over time, in weeks                                                                              Separation/                                 Ex.                                                                              Polymer                                                                            (°C.)                                                                         0  1   2   3   4   Precipitation                               __________________________________________________________________________    40 1    25     4.368                                                                            4.368                                                                             4.1184                                                                            4.4928                                                                            4.68                                                                              None                                        41 1    40     4.368                                                                            5.304                                                                             4.992                                                                             5.304                                                                             5.2416                                                                            None                                        42 5    25     4.68                                                                             5.2416                                                                            4.8048                                                                            5.304                                                                             5.4288                                                                            None                                        43 5    40     4.68                                                                             6.24                                                                              5.6784                                                                            6.24                                                                              6.24                                                                              None                                        C  None 25     5.304                                                                            5.5536                                                                            5.2416                                                                            4.992                                                                             5.3664                                                                            None                                        D  None 40     5.304                                                                            6.1776                                                                            5.616                                                                             5.928                                                                             5.8302                                                                            None                                        __________________________________________________________________________

The results demonstrate good storage stability for high pH formulationsof poly(N-acyl alkylenimines) in typical curl relaxer formulations, aswell as indicating utility in other high pH formulations such aspermanent wave products, and the like.

EXAMPLE 44-48 AND CONTROLS E-H FILM PROPERTIES

These examples demonstrate that the partially hydrolyzed, poly(N-acylalkylenimines), and derivatives thereof, have desirable film properties.The properties of such films change qualitatively depending upon themositure content absorbed in the film. Generally, at ambient such filmsare glossy, smooth and highly deformable. In contrast, cellulosicpolymers used in personal care, such as L_(MW) QNHEC and HEC are onlymoderately glossy and have a rougher surface due to fibers.Noncellulosics usable in personal care, such as ES-225, are very glossyand smooth but brittle under the same conditions.

The glossiness provided by such polymers, using the previously describedprocedure, are set forth in Table 6.

                  TABLE 6                                                         ______________________________________                                        FILM GLOSS RATINGS                                                                                Gloss Readings                                            Example     Polymer       20°                                                                           60°                                   ______________________________________                                        44          Example 8     5.1.sup.a                                                                            2.8.sup.a                                    45          Example 17    18.0   8.7                                          46          Example 19    27.6   5.3                                          47          Example 20    20.3   6.1                                          48          Example 21    23.1   3.7                                          E           ES-225        26.3   5.0                                          F           GAF-937       20.1   5.0                                          G           L.sub.MW QNHEC                                                                              14.2   3.5                                          H           HEC           10.3   2.8                                          ______________________________________                                         .sup.a low gloss attributed to high salt content in polymer.             

The results demonstrate that partially hydrolyzed, poly(N-acylalkylenimine) provide equivalent to superior gloss readings as comparedto commercially available, personal care polymers.

EXAMPLES 49-51 AND CONTROLS I-J HUMECTANCY

In these examples, the hygroscopicities of the specified partiallyhydrolyzed, poly(N-propionyl ethylenimines) are measured and comparedwith commercially available, personal care polymers, using thepreviously described procedures, with the results set forth in Table 7.

                  TABLE 7                                                         ______________________________________                                        EQUILIBRIUM MOISTURE CONTENT                                                              Moisture Retention (wt. %)                                        Example Polymer   35% RH     68% RH 78% RH                                    ______________________________________                                        49      Example 1 6.8        18.9   29.3                                      50      Example 2 6.7        18.3   27.6                                      51      Example 3 7.1        18.2   28.9                                      I       ES-225    2          3      6.5                                       J       HEC       5          13     18                                        ______________________________________                                    

The results demonstrate partially hydrolyzed, poly(N-acyl alkylenimines)exhibit significant hygroscopicity, indicating utility in personal careformulations designed ot improve water retention, i.e., humectants.

EXAMPLES 52-55 AND CONTROL K SUBSTANTIVITY

In these examples, the substantivities of the partially hydrolyzed,poly(N-propionyl ethylenimines) produced in Examples 1-3 are analyzed.

Electrokinetic analysis, following procedures as described in Goddard etal. Proceedings of the 15th I.F.S.C.C. Congress, Volume 1, page 79(1984), of such partially hydrolyzed, poly(N-acyl alkylenimines)indicates that such polymers provide substantivity due to cationicpolymer structure attraction to the negatively charged keratinoussurface of the substrate.

The retention of partially hydrolyzed, poly(N-acyl alkylenimines) onhair tresses, prepared and tested using the previously describedprocedures, also provides evidence of substantivity. Hair tresses andcurls are prepared, through application of the specified polymersolutions for one minute with or without rinsing for 30 seconds inrunning deionized water, and tested with the results set forth in Table8.

                                      TABLE 8                                     __________________________________________________________________________    CURL RETENTION AND EVALUATION                                                              Curl Length, mm (% of control).sup.a                             Example                                                                            Polymer                                                                            pH Initial                                                                             After 30'                                                                           After 60'                                                                           Feel                                                                             Appearance                                  __________________________________________________________________________    52   Ex. 9                                                                              6.75                                                                             5.8(51%)                                                                            6.9(55%)                                                                            7.5(57%)                                                                            Stiff                                                                            Shiny                                            (Rinsed)                                                                              9.3(88%)                                                                             11(92%)                                                                             12(92%)                                                                            Mod.                                                                             Mod.                                                                       Stiff                                                                            Shiny                                       53   Ex. 20                                                                             8.36                                                                             --    --    --    -- --                                               (Rinsed)                                                                              11.8(104%)                                                                          13.2(106%)                                                                          13.9(106%)                                                                          Soft                                                                             Same.sup.b                                  54   Ex. 21                                                                             8.44                                                                             7.5(66%)                                                                            9.4(75%)                                                                            9.9(76%)                                                                            Stiff                                                                            Shiny                                            (Rinsed)                                                                              11.2(99%)                                                                           13.0(104%)                                                                          13.5(103%)                                                                          Soft                                                                             Same.sup.b                                  55   Ex. 22                                                                             8.64                                                                             5.7(50%)                                                                            6.7(54%)                                                                            7.0(53%)                                                                            Stiff                                                                            Shiny                                            (Rinsed)                                                                              9.9(88%)                                                                            11.5(92%)                                                                           12.0(92%)                                                                           Mod.                                                                             Mod.                                                                       Stiff                                                                            Shiny                                       K    None    11.3  12.5  13.1  -- --                                          __________________________________________________________________________     .sup.a parenthetical value describes treated curl length as a percentage      of curl length of untreated control in water.                                 .sup.b same as control                                                   

These results demonstrate that increased curl retention is provided byall the unrinsed polymer treatments, while substantivity is furtherestablished by the stiff feel and shiny appearance of the treated hair.In addition, higher molecular weight, partially hydrolyzed, poly(N-acylalkylenimines) provide increased curl retention, as well as modifiedfeel and appearance properties, in the rinsed treatments. The resultsdemonstrate substantivity through retention of the partially hydrolyzed,poly(N-acyl alkylenimine) upon application to hair, including afterrinse treatment.

EXAMPLE 56 Toxicity

In this example, a blend of poly(N-propionyl ethylenimine), producedfollowing the procedures in Example 8 except that the product isrecovered as a 21 weight precent aqueous solution instead of isolatingas a dry product and having a salt level of 6.94 wt. %, is evaluatedfollowing standard procedures for acute toxicity and primary irritancyanalysis. The polymer is of a very low order of acute peroral andpercutaneous toxicity, a low order of acute inhalation toxicity byexposure to its vapor generated at ambient temperature, and of minimalirritation to the skin and eye. Such polymers are therefore eminentlysuited to personal care applications.

We claim:
 1. A personal care composition comprising carrier and aneffective managing amount of partially hydrolyzed, poly(N-acylalkylenimine) containing repeating units represented by the structuralformula: ##STR9## wherein a is from about 1 to about 50 mole percent;and wherein for each repeating unit individually:Q is an anion; R₁ ishydrogen, alkyl, aryl, aralkyl or alkaryl; R₂ is hydrogen or ahydrocarbyl-containing group; R₃ is hydrogen, alkyl, aryl, aralkylo oralkaryl; v is equal to the valence of Q; x is 2 or 3; y is 0 or 1; and zis 0 or 1; provided that:(1) when R₃ is oxygen than y is 0, R₂ is ahydrcarbyl-containing group and z is 1; (2) when R₃ is not oxygen then yand z are 1; and (3) when all z values are 0 then at least one R₃ groupis a hydrocarbyl-containing group.
 2. The composition of claim 1 whereinall R₂ and R₃ are hydrogen.
 3. The composition of claim 1 wherein Qrepresents a mixture of anions.
 4. The composition of claim 1 wherein atleast one R₂ or R₃ is a hydrocarbyl-containing group.
 5. The compositionof claim 4 wherein at least one hydrocarbyl-conatining group has acationic or anionic group.
 6. The composition of claim 1 containing aneffective amount of one or more suitable personal care ingredientssufficient to provide a soap, shampoo, cream, lotion, hair spray, hairor skin conditioner, mousse, antiperspirant, deodorant, hair set, hairwave, hair straightener, make-up, shave cream or gel, after shave lotionor balm.
 7. The composition of claim 6 wherein said personal careingredient is a surfactant, cleanser, colorant, preservative,moisturizer, pH adjustor, emulsifier, propellant, conditioner,thickener, fragrance, foaming agent, sunscreen, depilatory, flavor,astringent agent, antiseptic, deodorant, antiperspirant, insectrepellant, bleach, anti-dandruff agent, adhesive, polish, strengthener,filler, barrier material, other personal care ingredient, or mixturesthereof.
 8. The composition of claim 1 wherein:a is from about 3 toabout 30 mole percent; Q is selected from the group consisting of:halides, phosphites, phosphonates, phosphates nitrates, sulfates,sulfonates, carbonates, carboxylates, or mixtures thereof; R₁ ishydrogen, methyl, ethyl or propyl; each R₂ and R₃ is individuallyhydrogen, alkyl, aryl, alkaryl, aralkyl or alkyloxy which isunsubstituted or substituted with hydroxyl, sulfonato, amino, ammonio,carboxyl, carboxylate, or mixtures thereof; and v is 1 or
 2. 9. Thecomposition of claim 1 wherein each R₁ is ethyl and each x is 2,providing the poly(N-propionyl ethylenimine) containing repeating unitsrepresented by the structural formula: ##STR10## wherein a, Q, R₂, R₃,v, y and z are as defined in claim
 1. 10. The composition of claim 9wherein:a is from about 3 to about 30 mole percent; Q is selected fromthe group consisting of: halides, phosphites, phosphonates, phosphates,nitrates, sulfates, sulfonates, carbonates, carboxylates, or mixturesthereof; each R₂ and R₃ is individually hydrogen, alkyl, aryl, alkaryl,aralkyl or alkyloxy which is unsubstituted or substituted with hydroxyl,sulfonato, amino, ammonio, carboxyl, carboxylate, or mixtures thereof;and v is 1 or
 2. 11. The composition of claim 10 wherein:a is about 12mole percent; Q is chloride, propionate, or mixtures thereof; each R₂and R₃ is individually hydrogen, 2-hydroxy-3-(trimethylammonio)propyl,2-hydroxy-3-(dimethyldodecylammonio)propyl, 2-hydroxy-3-sulfonatopropyl,2,3-dihydroxypropyl, or mixtures thereof; and v is
 1. 12. A process forproducing a personal care composition which comprises providing acarrier with an effective managing amount of partially hydrolyzed,poly(N-acyl alkylenimine) containing repeating units represented by thestructural formula: ##STR11## wherein a is from about 1 to about 50 molepercent; and wherein for each repeating unit individually:Q is an anion;R₁ is hydrogen, alkyl, aryl, aralkyl or alkaryl; R₂ is hydrogen or ahydrocarbyl-containing group; R₃ is hydrogen, oxygen or ahydrocarbyl-containing group; v is equal to the valence of Q; x is 2 or3; y is 0 is 1; and z is 0 or 1; provided that:(1) when R₃ is oxygenthen y is 0, R₂ is a hydrocarbyl-containing group and z is 1; (2) whenR₃ is not oxygen then y and z are 1; and (3) when all z values are 0then at least one R₃ group is a hydrocarbyl-containing group.
 13. Theprocess of claim 12 wherein:a is from about 3 to about 30 mole percent;Q is selected from the group consisting of: halides, phosphites,phosphonates, phosphates, nitrates, sulfates, sulfonates, carbonates,carboxylates, or mixtures thereof; each R₂ and R₃ is individuallyhydrogen, alkyl, aryl, alkaryl, aralkyl or alkyloxy which isunsubstituted or substituted with hydroxyl, sulfonato, amino, ammonio,carboxyl, carboxylate, or mixtures thereof; and v is 1 or
 2. 14. Theprocess of claim 13 wherein each R₁ is ethyl and each x value is 2providing the poly(N-propionyl ethylenimine) containing repeating unitsrepresented by the structural formula: ##STR12## wherein a, Q, R₂, R₃,v, y and z are as defined in claim
 12. 15. The process of claim 14wherein:a is about 12 mole percent; Q is chloride, propionate, ormixtures thereof; each R₂ and R₃ is individually hydrogen,2-hydroxy-3-(trimethylammonio)propyl,2-hydroxy-3-(dimethyldodecylammonio)propyl, 2-hydroxy-3-sulfonatopropyl,2,3-dihydroxypropyl, or mixtures thereof; and v is
 1. 16. A process formanaging keratinous substrate comprising applying to said substrate aneffective managing amount of partially hydrolyzed, poly(N-acylalkylenimine) containing repeating units represented by the structuralformula: ##STR13## wherein a is from about 1 to about 50 mole percent;and wherein for each repeating unit individually: Q is an anion;R₁ ishydrogen, alkyl, aryl, aralkyl or alkaryl; R₂ is hydrogen or ahydrocarbyl-containing group; R₃ is hydrogen, oxygen or ahydrocarbyl-containing group; v is equal to the valence of Q; x is 2 or3; y is 0 or 1 and z is 0 or 1; provided that:(1) when R₃ is oxygen thany is 0, R₂ is a hydrocarbyl-containing group and z is 1; (2) when R₃ isnot oxygen then y and z are 1; and (3) when all z values are 0 then atleast one R₃ group is a hydrocarbyl-containing group.
 17. The process ofclaim 16 wherein:a is from about 3 to about 30 mole percent; Q isselected from the group consisting of: halides, phosphites,phosphonates, phosphates, nitrates, sulfates, sulfonates, carbonates,carboxylates, or mixtures thereof; each R₂ and R₃ is individuallyhydrogen, alkyl, aryl, alkaryl, aralkyl or alkyloxy which isunsubstituted or substituted with hydroxyl, sulfonato, amino, ammonio,carboxyl, carboxylate, or mixtures thereof; and v is 1 or
 2. 18. Theprocess of claim 17 wherein each R₁ is ethyl and each x value is 2providing the poly(N-propionyl ethylenimine) containing repeating unitsrepresented by the structural formula: ##STR14## wherein a, Q, R₁, v, yand z are as defined in claim
 16. 19. The process of claim 18 wherein:ais about 12 mole percent; Q is chloride, propionate, or mixturesthereof; each R₂ and R₃ is individually hydrogen,2-hydroxy-3-(trimethylammonio)propyl,2-hydroxy-3-(dimethyldodecylammonio)propyl, 2-hydroxy-3-sulfonatopropyl,2,3-dihydroxypropyl, or mixtures thereof; and v is 1.